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United States Patent |
5,707,950
|
Kasturi
,   et al.
|
January 13, 1998
|
Detergent compositions containing lipase and protease
Abstract
The invention concerns laundry detergent compositions comprising lipase
(especially the variant D96L of the native lipase derived from Humicola
lanuginosa), protease, and surfactant, wherein said compositions comprise
levels of lipase enzyme and protease enzyme such that the whitening
performance of said compositions is increased. These compositions deliver
an improved whiteness maintenance and/or dingy clean-up on fabrics.
Inventors:
|
Kasturi; Chandrika (Fairfield, OH);
Baeck; Andre (Bonheiden, BE);
Wolff; Ann Margaret (Cincinnati, OH)
|
Assignee:
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The Procter & Gamble Company (Cincinnati, OH)
|
Appl. No.:
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729543 |
Filed:
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October 11, 1996 |
Current U.S. Class: |
510/320; 8/137; 510/392; 510/530 |
Intern'l Class: |
C11D 003/386 |
Field of Search: |
435/219-225,198,263,264
510/320,392,530
8/137
|
References Cited
U.S. Patent Documents
4769173 | Sep., 1988 | Cornelissen et al. | 252/174.
|
4810414 | Mar., 1989 | Hse-Jensens | 252/174.
|
5069809 | Dec., 1991 | Lagerwaard et al. | 252/174.
|
5078898 | Jan., 1992 | Jars | 252/174.
|
5100796 | Mar., 1992 | Paridans et al. | 435/198.
|
5185250 | Feb., 1993 | Brenner et al. | 435/69.
|
5204015 | Apr., 1993 | Caldwell et al. | 252/174.
|
5520835 | May., 1996 | Siuik et al. | 510/220.
|
5559089 | Sep., 1996 | Hartman et al. | 510/224.
|
Foreign Patent Documents |
218272 | Apr., 1987 | EP | .
|
271154 | Jun., 1988 | EP.
| |
381397 | Aug., 1990 | EP | .
|
405901 | Jan., 1991 | EP | .
|
0516200 | Dec., 1992 | EP.
| |
9205249 | Apr., 1992 | WO.
| |
WO 92/05249 | Apr., 1992 | WO | .
|
9211348 | Jul., 1992 | WO.
| |
9218599 | Oct., 1992 | WO.
| |
WO 93/23516 | Nov., 1993 | WO | .
|
WO 94/03578 | Feb., 1994 | WO | .
|
WO 94/10284 | May., 1994 | WO | .
|
WO 95/10591 | Apr., 1995 | WO | .
|
Other References
U.S. application No. 08/341826, Baeck et al. filed Nov., 18, 1994.
Malmos, Gormsen, "A New Lipase for the Detergent Industry", HAPPI
(Household & Personal Products Industry), vol. 28, No. 10, Oct. 1991, pp.
122-125.
Research Disclosure No. 35944 by NOVO, Mar. 10, 1994.
Research Disclosure, vol. 2244, No. 359, Mar. 1994 "Detergent Compositions
Comprising Lipase Variants", pp. 151-156.
|
Primary Examiner: Lieberman; Paul
Assistant Examiner: Fries; Kery A.
Attorney, Agent or Firm: Zerby; K. W., Yetter; J. J., Rasser; J. C.
Parent Case Text
This is a continuation of application Ser. No. 08/341,828, filed on Nov.
18, 1994 abandoned.
Claims
What is claimed is:
1. A laundry detergent composition comprising:
(a) from about 0.001% to about 2% of a lipase enzyme variant D96L of the
native lipase derived from Humicola lanuginosa strain D SM 4106;
(b) a protease enzyme selected from the group consisting of the Bacillus
lentus subtilisin variant N76D/S103A/V104I according to the numbering of
Bacillus amyloliquefaciens subtilisin at a level to provide from 0.005 to
0.1 AU per gram of composition; and
(c) from about 0.1% to about 60% of a surfactant;
and wherein further said compositions comprise levels of lipase enzyme and
protease enzyme such that the whitening performance of said compositions
is increased.
2. A method for laundering fabrics to maintain whiteness and provide dingy
cleanup, said method comprising contacting fabrics in need of whiteness
and dingy clean-up with an aqueous solution comprising the laundry
detergent composition according to claim 1, said aqueous solution
comprising the lipase enzyme at a level of from about 150 to about 5000 LU
per liter.
Description
FIELD OF THE INVENTION
The present invention relates to laundry detergent compositions containing
lipolytic enzyme, proteolytic enzyme, and surfactant, and the use of said
compositions in laundry cleaning processes to provide whiteness
maintenance and/or dingy clean-up.
BACKGROUND OF THE INVENTION
The inclusion of lipase in detergent compositions for improved cleaning
performance is known, e.g. enhancement of removal of triglycerides
containing soils and stains from fabrics. Examples are U.S. Pat. No.
4,769,173, Cornelissen et al. issued Aug. 29, 1989; U.S. Pat. No.
5,069,809, Lagerwaard et at., issued Dec. 3, 1991; PCT application
WO94/03578 and HAPPI (Household & Personal Products Industry) No. 28/1991.
In U.S. Pat. No. 4,769,173 is disclosed a certain class of lipases
consisting of fungal lipases ex Humicola lanuginosa together with strong
bleaching agents in detergent compositions. An example of a fungal lipase
in this patent is the lipase ex Humicola lanuginosa, available from Amano
under the tradename Arnano-CE.
In U.S. Pat. No. 5,069,809 is disclosed the combination of strong bleaching
agents with a lipase enzyme produced by cloning the gene encoding the
lipase produced by Humicola lanuginosa and expressing the gene in
Aspergillus oryzae as host for use in detergent compositions.
In WO 94/03578 is disclosed an enzymatic detergent composition containing
10 to 20 000 LU (Lipolytic units) per gram of detergent composition of a
lipase showing a substantial lipolytic activity during the main cycle of a
wash process. This lipase is selected in particular on its inactivation
behaviour with Diisopropyl Fluoro Phosphate (DFP).
Likewise, the inclusion of proteases in detergent compositions for improved
cleaning performance is known. For example, protease enzymes are described
in U.S. Pat. No. 5,185,250 and U.S. Pat. No. 5,204,015. In addition,
bleach compositions containing protease having enhanced stain removal
properties are also known, having been described in WO 94/10284, published
May 11, 1994, by The Procter & Gamble Company. Commercially available
protease enzymes include Alcalase.RTM., Esperase.RTM., Durazym.RTM.,
Savinase.RTM., Maxtase.RTM., Maxacal.RTM., and Maxapem.RTM. 15 (protein
engineered Maxacal); Purafect.RTM. and subtilisin BPN and BPN'.
Of the lipase enzymes, only the lipase derived from Humicola lanuginosa and
produced in Aspergillus oryzae as host has so far found wide-spread
application as additive for fabric washing products. It is available under
the tradename Lipolase.RTM., from Novo Nordisk. Gormsen and Malmos
describe in HAPPI Lipolase as being the first detergent lipase with a
commercially relevant cost performance based on the use of recombinant DNA
technology on an industrial scale.
In order to optimize the stain removal performance of Lipolase, Novo
Nordisk have made a number of variants. WO 92/05249 describes the D96L
variant of the native Humicola lanuginosa lipase improves the lard stain
removal efficiency by a factor 4.4 over the wild-type lipase (enzymes
compared in an amount ranging from 0.075 to 2.5 mg protein per liter).
Example 20 therein describes the storage stability of certain of these
lipases in liquid detergent compositions in the presence of the protease
Alcalase.RTM..
Research Disclosure No. 35944 published on Mar. 10, 1994, by Novo Nordisk
discloses that the lipase variant (D96L) may be added in an amount
corresponding to 0.001-100 mg lipase variant per liter of wash liquor. The
compositions therein are said to optionally comprise "one or more other
enzymes, such as amylase, cutinase, protease, cellulase, peroxidase, and
oxidase."
Finally, detergent compositions comprising combinations of Lipolase and
certain proteases are commercially known, for example in the U.S.
Tide.RTM. and in Europe Ariel.RTM. (both brands sold by The Procter &
Gamble Company).
However, the benefits of whiteness maintenance and dingy clean-up on
fabrics using combinations of lipase and protease, preferably low levels
of D96L lipase variant in detergent compositions, has not been previously
recognized.
It has been found that lipase enzymes can be combined with protease enzymes
in surfactant compositions to obtain surprisingly effective dingy soil
clean-up and/or whiteness maintenance benefits. Accordingly, it is an
object of the present invention to provide improved laundry cleaning
compositions using lipase enzymes, protease enzymes and surfactants. It is
another object herein to provide a means for removing dingy soils from
fabrics using laundry compositions containing lipase, protease, and
surfactant. It is a further object to provide a means for maintaining
whiteness of fabrics using laundry compositions containing lipase,
protease, and surfactant. These and other objects are secured herein, as
will be seen from the following disclosures.
SUMMARY OF THE INVENTION
The present invention relates to laundry detergent compositions comprising:
(a) a lipase enzyme other than Lipolase; (b) a protease enzyme other than
Alcalase.RTM.; and (c) a surfactant; and wherein further said compositions
comprise levels of lipase enzyme and protease enzyme such that the
whitening performance of said compositions is increased.
Preferred are solid (preferably granular) laundry detergent compositions
comprising: (a) a lipase enzyme variant D96L of the native lipase derived
from Humicola lanuginosa; (b) a protease enzyme; and (c) a surfactant; and
wherein further said compositions comprise levels of said lipase enzyme
and protease enzyme such that the whitening performance of said
compositions is increased.
Also preferred are laundry detergent compositions comprising: (a) a lipase
enzyme (preferably Lipolase and/or a lipase enzyme variant D96L of the
native lipase derived from Humicola lanuginosa); (b) a protease enzyme
which is derived from a precursor carbonyl hydrolase by substituting a
different amino acid for the amino acid residue at position in said
carbonyl hydrolase equivalent to position +76 (preferably in combination
with one or more amino acid residue positions equivalent to those selected
from the group consisting of+99, +101, +103, +104, +107, +123, +27, +105,
+109, +126, +128, +135, +156, +166, +195, +197, +204, +206, +210, +216,
+217, +218, +222, +260, +265, and/or +274) according to the numbering of
Bacillus amyloliquefaciens subtilisin; and (c) a surfactant; and wherein
further said compositions comprise levels of lipase enzyme and protease
enzyme such that the whitening performance of said compositions is
increased.
The preferred lipolytic enzyme variant D96L of native Humicola lanuginosa
lipase is preferably incorporated into detergent compositions at a level
of from 50 lipolytic units (LU) to 8500 LU per liter wash solution.
Finally, the present invention relates to methods for laundering fabrics to
maintain whiteness and provide dingy cleanup, said methods comprising
contacting fabrics in need of whiteness and dingy clean-up with an aqueous
solution of a composition comprising lipase enzyme and protease enzyme at
levels such that the whitening performance of said composition is
increased.
All percentages, ratios and proportions herein are by weight, unless
otherwise specified. All documents cited are, in relevant part,
incorporated herein by reference.
DETAILED DESCRIPTION OF THE INVENTION
Without limitation by theory, it is believed that dingy soils are the
result of combinations of fatty soils and particulate soils. Fatty soils
comprise lipids, proteins, and pigments that are deposited over time on
fabrics from contact with human or animal skin. The majority of lipids are
secreted from the sebaceous gland as sebum. Proteins and pigments from
skin fragments are liberated by the breakdown of skin cells. Particulate
soils comprise mostly airborne soil and floor/ground dust. It is believed
that sebum is the major soil present on laundry, and its removal is
important because unremoved fat acts as a matrix to hold particulate
soils. Further it is believed that compounds present in the sebum can
oxidize to contribute to yellowing of fabrics. Particulate soils include
topsoil and products produced during the incomplete combustion of
petroleum products. "Dingy clean-up", as used herein, means the ability of
a detergent composition to remove such dingy soil build-up, over one or
more washes, resulting in a measurable improvement in fabric appearance.
Whiteness maintenance is the monitoring of the whiteness of wash & wear
fabrics over a number of washing cycles. A good performing detergent has a
good whiteness maintenance profile, i.e. it ensures that the whiteness of
washed fabrics is maintained at a high level during the complete life
cycle of wearing & washing.
"Whitening performance", as used herein, means the relative ability of
laundry detergent compositions comprising both lipase and protease enzymes
(as compared versus the same compositions comprising only protease enzyme
or lipase enzyme, under whatever comparative test conditions are employed)
to produce dingy clean-up and/or whiteness maintenance results.
Lipase Enzymes:
Lipase enzymes which may be considered for inclusion in the detergent
compositions of the present invention include those produced by
microorganisms of the Pseudomonas group, such as Pseudomonas stutzeri ATCC
19.154, as disclosed in British Patent 1,372,034. Lipases include those
which show a positive immunological cross-reaction with the antibody of
the lipase, produced by the microorganism Pseudomonas fluorescens IAM
1057. This lipase is available from Amano Pharmaceutical Co. Ltd., Nagoya,
Japan, under the trade name Lipase P "Amano," hereinafter referred to as
"Amano-P". Lipases include M1 Lipase.sup.R and Lipomax.sup.R
(Gist-Brocades) and Lipolase.sup.R (Novo).
The lipases are normally incorporated in the detergent composition at
levels from 0.0001% to 2% of active enzyme by weight of the detergent
composition.
A preferred component of the detergent composition according to the
invention is the D96L lipolytic enzyme variant of the native lipase
derived from Humicola lanuginosa. Preferably the Humicola lanuginosa
strain DSM 4106 is used. This enzyme is preferably incorporated into the
composition in accordance with the invention at a level of from about 50
LU to about 8500 LU per liter wash solution. More preferably the variant
D96L is present at a level of from about 100 LU to about 7500 LU per liter
of wash solution, and most preferably at a level of flora about 150 LU to
about 5000 LU per liter of wash solution.
By D96L lipolytic enzyme variant is meant the lipase variant as described
in patent application WO 92/05249 viz. wherein the native lipase ex
Humicola lanuginosa aspartic acid (D) residue at position 96 is changed to
Leucine (L). According to this nomenclature said substitution of aspartic
acid to Leucine in position 96 is shown as: D96L.
To determine the activity of the enzyme D96L the standard LU assay was used
(Analytical method, internal Novo Nordisk number AF 95/6-GB 1991.02.07). A
substrate for D96L was prepared by emulsifying glycerine tributyrat
(Merck) using gum-arabic as emulsifier. Lipase activity was assayed at pH
7 using pH stat. method. One unit of lipase activity (LU/mg) is defined as
the amount needed to liberate one micromole fatty acid per minute.
The D96L variant of the native Humicola lanuginosa lipase has the
additional advantage of delivering a significant benefit in whiteness
maintenance when compared to the wildtype lipase.
Protease Enzymes
Protease enzymes are usually present at levels sufficient to provide from
0.005 to 0.1 Anson units (AU) of activity per gram of composition. The
protealytic enzyme can be of animal, vegetable or microorganism
(preferred) origin. More preferred is serine protealytic enzyme of
bacterial origin. Purified or nonpurified forms of enzyme may be used.
Protealytic enzymes produced by chemically or genetically modified mutants
are included by definition, as are close structural enzyme variants.
Particularly preferred by way of protealytic enzyme is bacterial serine
protealytic enzyme obtained from Bacillus, Bacillus subtilis and/or
Bacillus licheniformis. Suitable commercial protealytic enzymes which may
be considered for inclusion in the present invention compositions include
Alcalase.RTM., Esperase.RTM., Durazym.RTM., Savinase.RTM., Maxatase.RTM.,
Maxacal.RTM., and Maxapem.RTM. 15 (protein engineered Maxacal);
Purafect.RTM. and subtilisin BPN and BPN'.
Protealytic enzymes also encompass modified bacterial serine proteases,
such as those described in European Patent Application Serial Number 87
303761.8, filed Apr. 28, 1987 (particularly pages 17, 24 and 98), and
which is called herein "Protease B", and in European Patent Application
199,404, Venegas, published Oct. 29, 1986, which refers to a modified
bacterial serine protealytic enzyme which is called "Protease A" herein.
More preferred is what is called herein "Protease C", which is a variant
of an alkaline serine protease from Bacillus in which lysine replaced
arginine at position 27, tyrosine replaced valine at position 104, serine
replaced asparagine at position 123, and alanine replaced threonine at
position 274. Protease C is described in EP 90915958:4, corresponding to
WO 91/06637, Published May 16, 1991, which is incorporated herein by
reference. Genetically modified variants, particularly of Protease C, are
also included herein.
Preferred protealytic enzymes are selected from the group consisting of
Savinase.RTM., Esperase.RTM., Maxacal.RTM., Purafect.RTM., BPN', Protease
A and Protease B, and mixtures thereof. Bacterial serine protease enzymes
obtained from Bacillus subtilis and/or Bacillus licheniformis are
preferred.
An especially preferred protease herein referred to as "Protease D" is a
carbonyl hydrolase variant having an amino acid sequence not found in
nature, which is derived from a precursor carbonyl hydrolase by
substituting a different amino acid for the amino acid residue at a
position in said carbonyl hydrolase equivalent to position +76, preferably
also in combination with one or more amino acid residue positions
equivalent to those selected from the group consisting of +99, +101, +103,
+104, +107, +123, +27, +105, +109, +126, +128, +135, +156, +166, +195,
+197, +204, +206, +210, +216, +217, +218, +222, +260, +265, and/or +274
according to the numbering of Bacillus amyloliquefaciens subtilisin, as
described in the concurrently filed patent application of A. Baeck et at.
entitled "Protease-Containing Cleaning Compositions" having U.S. Ser. No.
08/322,676, filed Oct. 13, 1994, which is incorporated herein by reference
in its entirety.
Surfactants
The detergent compositions according to the present invention comprise a
surfactant system wherein the surfactant can be selected from nonionic
and/or anionic and/or cationic and/or ampholytic and/or zwitterionic
and/or semi-polar surfactants.
The surfactant is typically present at a level of from 0.1% to 60% by
weight. More preferred levels of incorporation are 1% to 35% by weight,
most preferably from 1% to 20% by weight of machine laundry and rinse
added fabric softener compositions in accord with the invention.
The surfactant is preferably formulated to be compatible with enzyme
components present in the composition. In liquid or gel compositions the
surfactant is most preferably formulated such that it promotes, or at
least does not degrade, the stability of any enzyme in these compositions.
Preferred non-alkylbenzene sulfonate surfactant systems to be used
according to the present invention comprise as a surfactant one or more of
the nonionic and/or anionic surfactants described herein.
Polyethylene, polypropylene, and polybutylene oxide condensates of alkyl
phenols are suitable for use as the nonionic surfactant of the surfactant
systems of the present invention, with the polyethylene oxide condensates
being preferred. These compounds include the condensation products of
alkyl phenols having an alkyl group containing from about 6 to about 14
carbon atoms, preferably from about 8 to about 14 carbon atoms, in either
a straight-chain or branched-chain configuration with the alkylene oxide.
In a preferred embodiment, the ethylene oxide is present in an amount
equal to from about 2 to about 25 moles, more preferably from about 3 to
about 15 moles, of ethylene oxide per mole of alkyl phenol. Commercially
available nonionic surfactants of this type include Igepal.TM. CO-630,
marketed by the GAF Corporation; and Triton.TM. X-45, X-114, X-100 and
X-102, all marketed by the Rohm & Haas Company. These surfactants are
commonly referred to as alkylphenol alkoxylates (e.g., alkyl phenol
ethoxylates).
The condensation products of primary and secondary aliphatic alcohols with
from about 1 to about 25 moles of ethylene oxide are suitable for use as
the nonionic surfactant of the nonionic surfactant systems of the present
invention. The alkyl chain of the aliphatic alcohol can either be straight
or branched, primary or secondary, and generally contains from about 8 to
about 22 carbon atoms. Preferred are the condensation products of alcohols
having an alkyl group containing from about 8 to about 20 carbon atoms,
more preferably from about 10 to about 18 carbon atoms, with from about 2
to about 10 moles of ethylene oxide per mole of alcohol. About 2 to about
7 moles of ethylene oxide and most preferably from 2 to 5 moles of
ethylene oxide per mole of alcohol are present in said condensation
products. Examples of commercially available nonionic surfactants of this
type include Tergitol.TM. 15-S-9 (the condensation product of C.sub.11
-C.sub.15 linear alcohol with 9 moles ethylene oxide), Tergitol.TM. 24-L-6
NMW (the condensation product of C.sub.12 -C.sub.14 primary alcohol with 6
moles ethylene oxide with a narrow molecular weight distribution), both
marketed by Union Carbide Corporation; Neodol.TM. 45-9 (the condensation
product of C.sub.14 -C.sub.15 linear alcohol with 9 moles of ethylene
oxide), Neodol.TM. 23-3 (the condensation product of C.sub.12 -C.sub.13
linear alcohol with 3.0 moles of ethylene oxide), Neodol.TM. 45-7 (the
condensation product of C.sub.14 -C.sub.15 linear alcohol with 7 moles of
ethylene oxide), Neodol.TM. 45-5 (the condensation product of C.sub.14
-C.sub.15 linear alcohol with 5 moles of ethylene oxide) marketed by,
Shell Chemical Company, Kyro.TM. EOB (the condensation product of C.sub.13
-C.sub.15 alcohol with 9 moles ethylene oxide), marketed by The Procter &
Gamble Company, and Genapol LA O5O (the condensation product of C.sub.12
-C.sub.14 alcohol with 5 moles of ethylene oxide) marketed by Hoechst.
Preferred range of HLB in these products is from 8-11 and most preferred
from 8-10.
Also useful as the nonionic surfactant of the surfactant systems of the
present invention are the alkylpolysaccharides disclosed in U.S. Pat. No.
4,565,647, Llenado, issued Jan. 21, 1986, having a hydrophobic group
containing from about 6 to about 30 carbon atoms, preferably from about 10
to about 16 carbon atoms and a polysaccharide, e.g. a polyglycoside,
hydrophilic group containing from about 1.3 to about 10, preferably from
about 1.3 to about 3, most preferably from about 1.3 to about 2.7
saccharide units. Any reducing saccharide containing 5 or 6 carbon atoms
can be used, e.g., glucose, galactose and galactosyl moieties can be
substituted for the glucosyl moieties (optionally the hydrophobic group is
attached at the 2-, 3-, 4-, etc. positions thus giving a glucose or
galactose as opposed to a glucoside or galactoside). The intersaccharide
bonds can be, e.g., between the one position of the additional saccharide
units and the 2-, 3-, 4-, and/or 6- positions on the preceding saccharide
units.
The preferred alkylpolyglycosides have the formula
R.sup.2 O(C.sub.n H.sub.2n O).sub.t (glycosyl).sub.x
wherein R.sup.2 is selected from the group consisting of alkyl,
alkylphenyl, hydroxyalkyl, hydroxyalkylphenyl, and mixtures thereof in
which the alkyl groups contain from about 10 to about 18, preferably from
about 12 to about 14, carbon atoms; n is 2 or 3, preferably 2; t is from 0
to about 10, preferably 0; and x is from about 1.3 to about 10, preferably
from about 1.3 to about 3, most preferably from about 1.3 to about 2.7.
The glycosyl is preferably derived from glucose. To prepare these
compounds, the alcohol or alkylpolyethoxy alcohol is formed first and then
reacted with glucose, or a source of glucose, to form the glucoside
(attachment at the 1-position). The additional glycosyl units can then be
attached between their 1-position and the preceding glycosyl units 2-, 3-,
4- and/or 6-position, preferably predominately the 2-position.
The condensation products of ethylene oxide with a hydrophobic base formed
by the condensation of propylene oxide with propylene glycol are also
suitable for use as the additional nonionic surfactant systems of the
present invention. The hydrophobic portion of these compounds will
preferably have a molecular weight of from about 1500 to about 1800 and
will exhibit water insolubility. The addition of polyoxyethylene moieties
to this hydrophobic portion tends to increase the water solubility of the
molecule as a whole, and the liquid character of the product is retained
up to the point where the polyoxyethylene content is about 50% of the
total weight of the condensation product, which corresponds to
condensation with up to about 40 moles of ethylene oxide. Examples of
compounds of this type include certain of the commercially-available
Pluronic.TM. surfactants, marketed by BASF.
Also suitable for use as the nonionic surfactant of the nonionic surfactant
system of the present invention, are the condensation products of ethylene
oxide with the product resulting from the reaction of propylene oxide and
ethylenediamine. The hydrophobic moiety of these products consists of the
reaction product of ethylenediamine and excess propylene oxide, and
generally has a molecular weight of from about 2500 to about 3000. This
hydrophobic moiety is condensed with ethylene oxide to the extent that the
condensation product contains from about 40% to about 80% by weight of
polyoxyethylene and has a molecular weight of from about 5,000 to about
11,000. Examples of this type of nonionic surfactant include certain of
the commercially available Tetronic.TM. compounds, marketed by BASF.
Preferred for use as the nonionic surfactant of the surfactant systems of
the present invention are polyethylene oxide condensates of alkyl phenols,
condensation products of primary and secondary aliphatic alcohols with
from about 1 to about 25 moles of ethylene oxide, alkylpolysaccharides,
and mixtures thereof. Most preferred are C.sub.8 -C.sub.14 alkyl phenol
ethoxylates having from 3 to 15 ethoxy groups and C.sub.8 -C.sub.18
alcohol ethoxylates (preferably C.sub.10 avg.) having from 2 to 10 ethoxy
groups, and mixtures thereof.
Highly preferred nonionic surfactants are polyhydroxy fatty acid amide
surfactants of the formula.
##STR1##
wherein R.sup.1 is H, or R.sup.1 is C.sub.1-4 hydrocarbyl, 2-hydroxy
ethyl, 2-hydroxy propyl or a mixture thereof, R.sup.2 is C.sub.5-31
hydrocarbyl, and Z is a polyhydroxyhydrocarbyl having a linear hydrocarbyl
chain with at least 3 hydroxyls directly connected to the chain, or an
alkoxylated derivative thereof. Preferably, R.sup.1 is methyl, R.sup.2 is
a straight C.sub.11-15 alkyl or C.sub.16-18 alkyl or alkenyl chain such as
coconut alkyl or mixtures thereof, and Z is derived from a reducing sugar
such as glucose, fructose, maltose, lactose, in a reductive amination
reaction.
When included in such laundry detergent compositions, the nonionic
surfactant systems of the present invention act to improve the greasy/oily
stain removal properties of such laundry detergent compositions across a
broad range of laundry conditions.
Highly preferred anionic surfactants include alkyl alkoxylated sulfate
surfactants hereof are water soluble salts or acids of the formula
RO(A).sub.m SO3M wherein R is an unsubstituted C.sub.10 -C.sub.24 alkyl or
hydroxyalkyl group having a C.sub.10 -C.sub.24 alkyl component, preferably
a C.sub.12 -C.sub.20 alkyl or hydroxyalkyl, more preferably C.sub.12
-C.sub.18 alkyl or hydroxyalkyl, A is an ethoxy or propoxy unit, m is
greater than zero, typically between about 0.5 and about 6, more
preferably between about 0.5 and about 3, and M is H or a cation which can
be, for example, a metal cation (e.g., sodium, potassium, lithium,
calcium, magnesium, etc.), ammonium or substituted-ammonium cation. Alkyl
ethoxylated sulfates as well as alkyl propoxylated sulfates are
contemplated herein. Specific examples of substituted ammonium cations
include methyl-, dimethyl, trimethyl-ammonium cations and quaternary
ammonium cations such as tetramethyl-ammonium and dimethyl piperdinium
cations and those derived from alkylamines such as ethylamine,
diethylamine, triethylamine, mixtures thereof, and the like. Exemplary
surfactants are C.sub.12 -C.sub.18 alkyl polyethoxylate (1.0) sulfate
(C.sub.12 -C.sub.18 E(1.0)M), C.sub.12 -C.sub.18 alkyl polyethoxylate
(2.25) sulfate (C.sub.12 -C.sub.18 E(2.25)M), C.sub.12 -C.sub.18 alkyl
polyethoxylate (3.0) sulfate (C.sub.12 -C.sub.18 E(3.0)M), and C.sub.12
-C.sub.18 alkyl polyethoxylate (4.0) sulfate (C.sub.12 -C.sub.18 E(4.0)M),
wherein M is conveniently selected from sodium and potassium.
Suitable anionic surfactants to be used are alkyl ester sulfonate
surfactants including linear esters of C.sub.8 -C.sub.20 carboxylic acids
(i.e., fatty acids) which are sulfonated with gaseous SO.sub.3 according
to "The Journal of the American Oil Chemists Society", 52 (1975), pp.
323-329. Suitable starting materials would include natural fatty
substances as derived from tallow, palm oil, etc.
The preferred alkyl ester sulfonate surfactant, especially for laundry
applications, comprise alkyl ester sulfonate surfactants of the structural
formula:
##STR2##
wherein R.sup.3 is a C.sub.8 -C.sub.20 hydrocarbyl, preferably an alkyl,
or combination thereof, R.sup.4 is a C.sub.1 -C.sub.6 hydrocarbyl,
preferably an alkyl, or combination thereof, and M is a cation which forms
a water soluble salt with the alkyl ester sulfonate. Suitable salt-forming
cations include metals such as sodium, potassium, and lithium, and
substituted or unsubstituted ammonium cations, such as monoethanolamine,
diethanolamine, and triethanolamine. Preferably, R.sup.3 is C.sub.10
-C.sub.16 alkyl, and R.sup.4 is methyl, ethyl or isopropyl. Especially
preferred are the methyl ester sulfonates wherein R.sup.3 is C.sub.10
-C.sub.16 alkyl.
Other suitable anionic surfactants include the alkyl sulfate surfactants
which are water soluble salts or acids of the formula ROSO3M wherein R
preferably is a C.sub.10 -C.sub.24 hydrocarbyl, preferably an alkyl or
hydroxyalkyl having a C.sub.10 -C.sub.20 alkyl component, more preferably
a C.sub.12 -C.sub.18 alkyl or hydroxyalkyl, and M is H or a cation, e.g.,
an alkali metal cation (e.g. sodium, potassium, lithium), or ammonium or
substituted ammonium (e.g. methyl-, dimethyl-, and trimethyl ammonium
cations and quaternary ammonium cations such as tetramethyl-ammonium and
dimethyl piperdinium cations and quaternary ammonium cations derived from
alkylamines such as ethylamine, diethylamine, triethylamine, and mixtures
thereof, and the like). Typically, alkyl chains of C.sub.12 -C.sub.16 are
preferred for lower wash temperatures (e.g. below about 50.degree. C.) and
C.sub.16-18 alkyl chains are preferred for higher wash temperatures (e.g.
above about 50.degree. C.).
Other anionic surfactants useful for detersive purposes can also be
included in the laundry detergent compositions of the present invention.
These can include salts (including, for example, sodium, potassium,
ammonium, and substituted ammonium salts such as mono-, di- and
triethanolamine salts) of soap, C.sub.8 -C.sub.22 primary of secondary
alkanesulfonates, C.sub.8 -C.sub.24 olefinsulfonates, sulfonated
polycarboxylic acids prepared by sulfonation of the pyrolyzed product of
alkaline earth metal citrates, e.g., as described in British patent
specification No. 1,082,179, C.sub.8 -C.sub.24
alkylpolyglycolethersulfates (containing up to 10 moles of ethylene
oxide); alkyl glycerol sulfonates, fatty acyl glycerol sulfonates, fatty
oleyl glycerol sulfates, alkyl phenol ethylene oxide ether sulfates,
paraffin sulfonates, alkyl phosphates, isethionates such as the acyl
isethionates, N-acyl taurates, alkyl succinamates and sulfosuccinates,
monoesters of sulfosuccinates (especially saturated and unsaturated
C.sub.12 -C.sub.18 monoesters) and diesters of sulfosuccinates (especially
saturated and unsaturated C.sub.6 -C.sub.12 diesters), acyl sarcosinates,
sulfates of alkylpolysaccharides such as the sulfates of
alkylpolyglucoside (the nonionic nonsulfated compounds being described
below), branched primary alkyl sulfates, and alkyl polyethoxy carboxylates
such as those of the formula RO(CH.sub.2 CH.sub.20).sub.k --CH.sub.2
COO--M+ wherein R is a C.sub.8 -C.sub.22 alkyl, k is an integer from 1 to
10, and M is a soluble salt-forming cation. Resin acids and hydrogenated
resin acids are also suitable, such as rosin, hydrogenerated rosin, and
resin acids and hydrogenated resin acids present in or derived from tall
oil.
Further examples are described in "Surface Active Agents and Detergents"
(Vol. I and II by Schwartz, Perry and Berch). A variety of such
surfactants are also generally disclosed in U.S. Pat. No. 3,929,678,
issued Dec. 30, 1975 to Laughlin, et al. at Column 23, line 58 through
Column 29, line 23 (herein incorporated by reference). When included
therein, the laundry detergent compositions of the present invention
typically comprise from about 1% to about 40%, preferably from about 3% to
about 20% by weight of such anionic surfactants.
The laundry detergent compositions of the present invention may also
contain cationic, ampholytic, zwitterionic, and semi-polar surfactants, as
well as the nonionic and/or anionic surfactants other than those already
described herein. Cationic detersive surfactants suitable for use in the
laundry detergent compositions of the present invention are those having
one long-chain hydrocarbyl group. Examples of such cationic surfactants
include the ammonium surfactants such as alkyltrimethylammonium
halogenides, and those surfactants having the formula:
›R.sup.2 (OR.sup.3).sub.y !›R.sup.4 (OR.sup.3).sub.y !.sub.2 R.sup.5 N+X--
wherein R.sup.2 is an alkyl or alkyl benzyl group having from about 8 to
about 18 carbon atoms in the alkyl chain, each R.sup.3 is selected from
the group consisting of --CH.sub.2 CH.sub.2 --, --CH.sub.2 CH(CH.sub.3)--,
--CH.sub.2 CH(CH.sub.2 OH)--, --CH.sub.2 CH.sub.2 CH.sub.2 --, and
mixtures thereof; each R.sup.4 is selected from the group consisting of
C.sub.1 -C.sub.4 alkyl, C.sub.1 -C.sub.4 hydroxyalkyl, benzyl ring
structures formed by joining the two R.sup.4 groups, --CH.sub.2
CHOH--CHOHCOR.sup.6 CHOHCH.sub.2 OH wherein R.sup.6 is any hexose or
hexose polymer having a molecular weight less than about 1000, and
hydrogen when y is not 0; R.sup.5 is the same as R.sup.4 or is an alkyl
chain wherein the total number of carbon atoms of R.sup.2 plus R.sup.5 is
not more than about 18; each y is from 0 to about 10 and the sum of the y
values is from 0 to about 15; and X is any compatible anion.
Highly preferred cationic surfactants are the water-soluble quaternary
ammonium compounds useful in the present composition having the formula:
R.sub.1 R.sub.2 R.sub.3 R.sub.4 N.sup.+ X.sup.- (i)
wherein R.sub.1 is C.sub.8 -C.sub.16 alkyl, each of R.sub.2, R.sub.3 and
R.sub.4 is independently C.sub.1 -C.sub.4 alkyl, C.sub.1 -C.sub.4 hydroxy
alkyl, benzyl, and --(C.sub.2 H.sub.40).sub.x H where x has a value from 2
to 5, and X is an anion. Not more than one of R.sub.2, R.sub.3 or R.sub.4
should be benzyl. The preferred alkyl chain length for R.sub.1 is C.sub.12
-C.sub.15 particularly where the alkyl group is a mixture of chain lengths
derived from coconut or palm kernel fat or is derived synthetically by
olefin build up or OXO alcohols synthesis. Preferred groups for R.sub.2
R.sub.3 and R.sub.4 are methyl and hydroxyethyl groups and the anion X may
be selected from halide, methosulphate, acetate and phosphate ions.
Examples of suitable quaternary ammonium compounds of formulae (i) for use
herein are:
coconut trimethyl ammonium chloride or bromide;
coconut methyl dihydroxyethyl ammonium chloride or bromide;
decyl triethyl ammonium chloride;
decyl dimethyl hydroxyethyl ammonium chloride or bromide;
C.sub.12-15 dimethyl hydroxyethyl ammonium chloride or bromide;
coconut dimethyl hydroxyethyl ammonium chloride or bromide;
myristyl trimethyl ammonium methyl sulphate;
lauryl dimethyl benzyl ammonium chloride or bromide;
lauryl dimethyl (ethenoxy).sub.4 ammonium chloride or bromide;
choline esters (compounds of formula (i) wherein R.sub.1 is CH.sub.2
--CH.sub.2 --O--C(O)--C.sub.12-14 alkyl and R.sub.2 R.sub.3 R.sub.4 are
methyl);
di-alkyl imidazolines ›compounds of formula (i)!.
Other cationic surfactants useful herein are also described in U.S. Pat.
No. 4,228,044, Cambre, issued Oct. 14, 1980 and in European Patent
Application EP 000,224.
When included therein, the laundry detergent compositions of the present
invention typically comprise from 0.2% to about 25%, preferably from about
1% to about 8% by weight of such cationic surfactants.
Ampholytic surfactants are also suitable for use in the laundry detergent
compositions of the present invention. These surfactants can be broadly
described as aliphatic derivatives of secondary or tertiary amines, or
aliphatic derivatives of heterocyclic secondary and tertiary amines in
which the aliphatic radical can be straight- or branched-chain. One of the
aliphatic substituents contains at least about 8 carbon atoms, typically
from about 8 to about 18 carbon atoms, and at least one contains an
anionic water-solubilizing group, e.g. carboxy, sulfonate, sulfate. See
U.S. Pat. No. 3,929,678 to Laughlin et al., issued Dec. 30, 1975 at column
19, lines 18-35, for examples of ampholytic surfactants.
When included therein, the laundry detergent compositions of the present
invention typically comprise from 0.2% to about 15%, preferably from about
1% to about 10% by weight of such ampholytic surfactants.
Zwitterionic surfactants are also suitable for use in laundry detergent
compositions. These surfactants can be broadly described as derivatives of
secondary and tertiary amines, derivatives of heterocyclic secondary and
tertiary amines, or derivatives of quaternary ammonium, quaternary
phosphonium or tertiary sulfonium compounds. See U.S. Pat. No. 3,929,678
to Laughlin et al., issued Dec. 30, 1975 at column 19, line 38 through
column 22, line 48, for examples of zwitterionic surfactants.
When included therein, the laundry detergent compositions of the present
invention typically comprise from 0.2% to about 15%, preferably from about
1% to about 10% by weight of such zwitterionic surfactants.
Semi-polar nonionic surfactants are a special category of nonionic
surfactants which include water-soluble amine oxides containing one alkyl
moiety of from about 10 to about 18 carbon atoms and 2 moieties selected
from the group consisting of alkyl groups and hydroxyalkyl groups
containing from about 1 to about 3 carbon atoms; water-soluble phosphine
oxides containing one alkyl moiety of from about 10 to about 18 carbon
atoms and 2 moieties selected from the group consisting of alkyl groups
and hydroxyalkyl groups containing from about 1 to about 3 carbon atoms;
and water-soluble sulfoxides containing one alkyl moiety of from about 10
to about 18 carbon atoms and a moiety selected from the group consisting
of alkyl and hydroxyalkyl moieties of from about 1 to about 3 carbon
atoms.
Semi-polar nonionic detergent surfactants include the amine oxide
surfactants having the formula
##STR3##
wherein R.sup.3 is an alkyl, hydroxyalkyl, or alkyl phenyl group or
mixtures thereof containing from about 8 to about 22 carbon atoms; R.sup.4
is an alkylene or hydroxyalkylene group containing from about 2 to about 3
carbon atoms or mixtures thereof; x is from 0 to about 3; and each R.sup.5
is an alkyl or hydroxyalkyl group containing from about 1 to about 3
carbon atoms or a polyethylene oxide group containing from about 1 to
about 3 ethylene oxide groups. The R.sup.5 groups can be attached to each
other, e.g., through an oxygen or nitrogen atom, to form a ring structure.
These amine oxide surfactants in particular include C.sub.10 -C.sub.18
alkyl dimethyl amine oxides and C.sub.8 -C.sub.12 alkoxy ethyl dihydroxy
ethyl amine oxides.
When included therein, the laundry detergent compositions of the present
invention typically comprise from 0.2% to about 15%, preferably from about
1% to about 10% by weight of such semi-polar nonionic surfactants.
Detergent Components
The detergent compositions of the invention may also contain additional
detergent components. The precise nature of these additional components,
and levels of incorporation thereof will depend on the physical form of
the composition, and the nature of the cleaning operation for which it is
to be used.
The compositions of the invention may for example, be formulated as hand
and machine laundry detergent compositions including laundry additive
compositions and compositions suitable for use in the pretreatment of
stained fabrics, and rinse added fabric softener compositions.
When formulated as compositions suitable for use in a machine washing
method, the compositions of the invention preferably contain both a
surfactant and a builder compound and additionally one or more detergent
components preferably selected from organic polymeric compounds, bleaching
agents, additional enzymes, suds suppressors, dispersants, lime-soap
dispersants, soil suspension and anti-redeposition agents and corrosion
inhibitors. Laundry compositions can also contain softening agents, as
additional detergent components.
If needed the density of the laundry detergent compositions herein ranges
from 550 to 1000 g/liter, preferably 600 to 950 g/liter of composition
measured at 20.degree. C.
The "compact" form of the compositions herein is best reflected by density
and, in terms of composition, by the amount of inorganic filler salt;
inorganic filler salts are conventional ingredients of detergent
compositions in powder form; in conventional detergent compositions, the
filler salts are present in substantial mounts, typically 17-35% by weight
of the total composition.
In the compact compositions, the filler salt is present in mounts not
exceeding 15% of the total composition, preferably not exceeding 10%, most
preferably not exceeding 5% by weight of the composition.
The inorganic filler salts, such as meant in the present compositions are
selected from the alkali and alkaline-earth-metal salts of sulphates and
chlorides. A preferred filler salt is sodium sulphate.
Optional Detergent Ingredients:
Preferred detergent compositions of the present invention may further
comprise an enzyme which provides cleaning performance and/or fabric care
benefits. Said enzymes include enzymes selected from cellulases,
hemicellulases, peroxidases, gluco-amylases, amylases, cutinases,
pectinases, xylanases, reductases, oxidases, phenoloxidases,
lipoxygenases, ligninases, pullulanases, tannases, pentosanases,
malanases, .beta.-glucanases, arabinosidases or mixtures thereof.
A preferred combination is a detergent composition having a cocktail of
conventional applicable enzymes like amylase, cutinase and/or cellulase in
conjunction with the lipolytic and protealytic enzymes.
The cellulases usable in the present invention include both bacterial or
fungal cellulase. Preferably, they will have a pH optimum of between 5 and
9.5. Suitable cellulases are disclosed in U.S. Pat. No. 4,435,307,
Barbesgoard et al, which discloses fungal cellulase produced from Humicola
insolens. Suitable cellulases are also disclosed in GB-A-2.075.028;
GB-A-2.095.275 and DE-OS-2.247.832.
Examples of such cellulases are cellulases produced by a strain of Humicola
insolens (Humicola grisea var. thermoidea), particularly the Humicola
strain DSM 1800.
Other suitable cellulases are cellulases originated from Humicola insolens
having a molecular weight of about 50 KDa, an isoelectric point of 5.5 and
containing 415 amino acids. Especially suitable cellulases are the
cellulases having color care benefits. Examples of such cellulases are
cellulases described in European patent application No. 91202879.2, filed
Nov. 6, 1991 (Novo).
Peroxidase enzymes are used in combination with oxygen sources, e.g.
percarbonate, perborate, persulfate, hydrogen peroxide, etc. They are used
for "solution bleaching", i.e. to prevent transfer of dyes or pigments
removed from substrates during wash operations to other substrates in the
wash solution.
Peroxidase enzymes are known in the art, and include, for example,
horseradish peroxidase, ligninase, and haloperoxidase such as chloro- and
bromo-peroxidase. Peroxidase-containing detergent compositions are
disclosed, for example, in PCT International Application WO 89/099813 and
in European Patent application EP No. 91202882.6, filed on Nov. 6, 1991.
Said cellulases and/or peroxidases are normally incorporated in the
detergent composition at levels from 0.0001% to 2% of active enzyme by
weight of the detergent composition.
Also suitable are cutinases ›EC 3.1.1.50! which can be considered as a
special kind of lipase, namely lipases which do not require interfacial
activation. Addition of cutinases to detergent compositions have been
described in e.g. WO-A-88/09367 (Genencor). The cutinases are normally
incorporated in the detergent composition at levels from 0.0001% to 2% of
active enzyme by weight of the detergent composition.
Amylases (& and/or .beta.) can be included for removal of
carbohydrate-based stains. Suitable amylases are Termamyl.sup.R (Novo
Nordisk), Fungamyl.sup.R and BAN.sup.R (Novo Nordisk). The above-mentioned
enzymes may be of any suitable origin, such as vegetable, animal,
bacterial, fungal and yeast origin.
Said enzymes are normally incorporated in the detergent composition at
levels from 0.0001% to 2% of active enzyme by weight of the detergent
composition. Other suitable detergent ingredients that can be added are
enzyme oxidation scavengers which are described in Copending European
Patent application 92870018.6 filed on Jan. 31, 1992. Examples of such
enzyme oxidation scavengers are ethoxylated tetraethylene polyamines.
Especially preferred detergent ingredients are combinations with
technologies which also provide a type of color care benefit. Examples of
these technologies are metallo catalysts for color maintenance. Such
metallo catalysts are described in copending European Patent Application
No. 92870181.2.
Additional optional detergent ingredients that can be included in the
detergent compositions of the present invention include bleaching agents
such as PB 1, PB4 and percarbonate with a particle size of 400-800
microns. These bleaching agent components can include one or more oxygen
bleaching agents and, depending upon the bleaching agent chosen, one or
more bleach activators. When present oxygen bleaching compounds will
typically be present at levels of from about 1% to about 25%. In general,
bleaching compounds are optional components in non-liquid formulations,
e.g. granular detergents.
The bleaching agent component for use herein can be any of the bleaching
agents useful for detergent compositions including oxygen bleaches as well
as others known in the art.
The bleaching agent suitabIe for the present invention can be an activated
or non-activated bleaching agent.
One category of oxygen bleaching agent that can be used encompasses
percarboxylic acid bleaching agents and salts thereof. Suitable examples
of this class of agents include magnesium monoperoxyphthalate hexahydrate,
the magnesium salt of meta-chloro perbenzoic acid,
4-nonylamino-4-oxoperoxybutyric acid and diperoxydodecanedioic acid. Such
bleaching agents are disclosed in U.S. Pat. No. 4,483,781, U.S. patent
application Ser. No. 740,446, European Patent Application 0,133,354 and
U.S. Pat. No. 4,412,934. Highly preferred bleaching agents also include
6-nonylamino-6-oxoperoxycaproic acid as described in U.S. Pat. No.
4,634,551.
Another category of bleaching agents that can be used encompasses the
halogen bleaching agents. Examples of hypohalite bleaching agents, for
example, include trichloro isocyanuric acid and the sodium and potassium
dichloroisocyanurates and N-chloro and N-bromo alkane sulphonamides. Such
materials are normally added at 0.5-10% by weight of the finished product,
preferably 1-5% by weight.
The hydrogen peroxide releasing agents can be used in combination with
bleach activators such as tetraacetylethylenediamine (TAED),
nonanoyloxybenzene-sulfonate (NOBS, described in U.S. Pat. No. 4,412,934),
3,5,-trimethylhexanoloxybenzenesulfonate (ISONOBS, described in EP
120,591) or pentaacetylglucose (PAG), which are perhydrolyzed to form a
peracid as the active bleaching species, leading to improved bleaching
effect. Also suitable activators are acylated citrate esters such as
disclosed in Copending European Patent Application No. 91870207.7.
Useful bleaching agents, including peroxyacids and bleaching systems
comprising bleach activators and peroxygen bleaching compounds for use in
cleaning compositions according to the invention are described in our
co-pending application U.S. Ser. No. 08/136,626.
The hydrogen peroxide may also be present by adding an enzymatic system
(i.e. an enzyme and a substrate therefore) which is capable of generating
hydrogen peroxide at the beginning or during the washing and/or rinsing
process. Such enzymatic systems are disclosed in EP Patent Application
91202655.6 filed Oct. 9, 1991.
Bleaching agents other than oxygen bleaching agents are also known in the
art and can be utilized herein. One type of non-oxygen bleaching agent of
particular interest includes photoactivated bleaching agents such as the
sulfonated zinc and/or aluminum phthalocyanines. These materials can be
deposited upon the substrate during the washing process. Upon irradiation
with light, in the presence of oxygen, such as by hanging clothes out to
dry in the daylight, the sulfonated zinc phthalocyanine is activated and,
consequently, the substrate is bleached. Preferred zinc phthalocyanine and
a photoactivated bleaching process are described in U.S. Pat. No.
4,033,718. Typically, detergent compositions will contain about 0.025% to
about 1.25%, by weight, of sulfonated zinc phthalocyanine.
The compositions according to the present invention may further comprise a
builder system. Any conventional builder system is suitable for use herein
including aluminosilicate materials, silicates, polycarboxylates and fatty
acids, materials such as ethylenediamine tetraacetate, metal ion
sequestrants such as aminopolyphosphonates, particularly ethylenediamine
tetramethylene phosphortic acid and diethylene triamine
pentamethylenephosphonic acid. Though less preferred for obvious
environmental reasons, phosphate builders can also be used herein.
Suitable builders can be an inorganic ion exchange material, commonly an
inorganic hydrated aluminosilicate material, more particularly a hydrated
synthetic zeolite such as hydrated zeolite A, X, B, HS or MAP.
Another suitable inorganic builder material is layered silicate, e.g. SKS-6
(Hoechst). SKS-6 is a crystalline layered silicate consisting of sodium
silicate (Na.sub.2 Si.sub.2 O.sub.5).
Suitable polycarboxylates containing one carboxy group include lactic acid,
glycolic acid and ether derivatives thereof as disclosed in Belgian Patent
Nos. 831,368, 821,369 and 821,370. Polycarboxylates containing two carboxy
groups include the water-soluble salts of succinic acid, malonic acid,
(ethylenedioxy) diacetic acid, maleic acid, diglycollic acid, tartaric
acid, tartronic acid and fumaric acid, as well as the ether carboxylates
described in German Offenlegenschrift 2,446,686, and 2,446,687 and U.S.
Pat. No. 3,935,257 and the sulfinyl carboxylates described in Belgian
Patent No. 840,623. Polycarboxylates containing three carboxy groups
include, in particular, water-soluble citrates, aconitrates and
citraconates as well as succinate derivatives such as the
carboxymethyloxysuccinates described in British Patent No. 1,379,241,
lactoxysuccinates described in Netherlands Application 7205873, and the
oxypolycarboxylate materials such as 2-oxa-1,1,3-propane tricarboxylates
described in British Patent No. 1,387,447.
Polycarboxylates containing four carboxy groups include oxydisuccinates
disclosed in British Patent No. 1,261,829, 1,1,2,2-ethane
tetracarboxylates, 1, 1,3,3-propane tetracarboxylates and 1,1,2,3-propane
tetracarboxylates. Polycarboxylates containing sulfo substituents include
the sulfosuccinate derivatives disclosed in British Patent Nos. 1,398,421
and 1,398,422 and in U.S. Pat. No. 3,936,448, and the sulfonated pyrolysed
titrates described in British Patent No. 1,082,179, while polycarboxylates
containing phosphone substituents are disclosed in British Patent No.
1,439,000.
Alicyclic and heterocyclic polycarboxylates include cyclopentane-cis,cis,
cis-tetracarboxylates, cyclopentadienide pentacarboxylates,
2,3,4,5-tetrahydro-furan -cis, cis, cis-tetracarboxylates,
2,5-tetrahydro-furan -cis-dicarboxylates,
2,2,5,5-tetrahydrofuran-tetracarboxylates, 1,2,3,4,5,6-hexane
-hexacar-boxylates and and carboxymethyl derivatives of polyhydric
alcohols such as sorbitol, mannitol and xylitol. Aromatic
poly-carboxylates include mellitic acid, pyromellitic acid and the
phthalic acid derivatives disclosed in British Patent No. 1,425,343.
Of the above, the preferred polycarboxylates are hydroxycarboxylates
containing up to three carboxy groups per molecule, more particularly
citrates.
Preferred builder systems for use in the present compositions include a
mixture of a water-insoluble aluminosilicate builder such as zeolite A or
of a layered silicate (SKS-6), and a water-soluble carboxylate chelating
agent such as citric acid.
A suitable chelant for inclusion in the detergent compositions in
accordance with the invention is ethylenediamine-N,N'-disuccinic acid
(EDDS) or the alkali metal, alkaline earth metal, ammonium, or substituted
ammonium salts thereof, or mixtures thereof. Preferred EDDS compounds are
the free acid form and the sodium or magnesium salt thereof. Examples of
such preferred sodium salts of EDDS include Na.sub.2 EDDS and Na.sub.4
EDDS. Examples of such preferred magnesium salts of EDDS include MgEDDS
and Mg.sub.2 EDDS. The magnesium salts are the most preferred for
inclusion in compositions in accordance with the invention.
Preferred builder systems include a mixture of a water-insoluble
aluminosilicate builder such as zeolite A, and a watersoluble carboxylate
chelating agent such as citric acid. Other builder materials that can form
part of the builder system for use in granular compositions include
inorganic materials such as alkali metal carbonates, bicarbonates,
silicates, and organic materials such as the organic phosphonates, amino
polyalkylene phosphonates and amino polycarboxylates.
Other suitable water-soluble organic salts are the homo- or co-polymeric
acids or their salts, in which the polycarboxylic acid comprises at least
two carboxyl radicals separated from each other by not more than two
carbon atoms. Polymers of this type are disclosed in GB-A-1,596,756.
Examples of such salts are polyacrylates of MW 2000-5000 and their
copolymers with maleic anhydride, such copolymers having a molecular
weight of from 20,000 to 70,000, especially about 40,000.
Detergency builder salts are normally included in amounts of from 10% to
80% by weight of the composition preferably from 20% to 70% and most
usually from 30% to 60% by weight.
Another optional ingredient is a suds suppressor, exemplified by silicones,
and silica-silicone mixtures. Silicones can be generally represented by
alkylated polysiloxane materials while silica is normally used in finely
divided forms exemplified by silica aerogels and xerogels and hydrophobic
silicas of various types. These materials can be incorporated as
particulates in which the suds suppressor is advantageously releasably
incorporated in a water-soluble or water-dispersible, substantially
non-surface-active detergent impermeable carrier. Alternatively the suds
suppressor can be dissolved or dispersed in a liquid carrier and applied
by spraying on to one or more of the other components.
A preferred silicone suds controlling agent is disclosed in Bartollota et
al. U.S. Pat. No. 3,933,672. Other particularly useful suds suppressors
are the self-emulsifying silicone suds suppressors, described in German
Patent Application DTOS 2 646 126 published Apr. 28, 1977. An example of
such a compound is DC-544, commercially available from Dow Corning, which
is a siloxane-glycol copolymer. Especially preferred suds controlling
agent are the suds suppressor system comprising a mixture of silicone oils
and 2-alkyl-alcanols. Suitable 2-alkyl-alkanols are 2-butyl-octanol which
are commercially available under the trade name Isofol 12 R.
Such suds suppressor system are described in Copending European Patent
application N 92870174.7 filed 10 Nov., 1992.
Especially preferred silicone suds controlling agents are described in
Copending European Patent application No. 92201649.8. Said compositions
can comprise a silicone/silica mixture in combination with fumed nonporous
silica such as Aerosil.sup.R.
The suds suppressors described above are normally employed at levels of
from 0.001% to 2% by weight of the composition, preferably from 0.01% to
1% by weight.
Other components used in detergent compositions may be employed, such as
soil-suspending agents, soil-release agents, optical brighteners,
abrasives, bactericides, tarnish inhibitors, coloring agents, and/or
encapsulated or non-encapsulated perfumes.
Especially suitable encapsulating materials are water soluble capsules
which consist of a matrix of polysaccharide and polyhydroxy compounds such
as described in GB 1,464,616.
Other suitable water soluble encapsulating materials comprise dextrins
derived from ungelatinized starch acid-esters of substituted dicarboxylic
acids such as described in U.S. Pat. No. 3,455,838. These acid-ester
dextrins are, preferably, prepared from such starches as waxy maize, waxy
sorghum, sago, tapioca and potato. Suitable examples of said encapsulating
materials include N-Lok manufactured by National Starch. The N-Lok
encapsulating material consists of a modified maize starch and glucose.
The starch is modified by adding monofunctional substituted groups such as
octenyl succinic acid anhydride.
Antiredeposition and soil suspension agents suitable herein include
cellulose derivatives such as methylcellulose, carboxymethylcellulose and
hydroxyethylcellulose, and homo- or co-polymeric polycarboxylic acids or
their salts. Polymers of this type include the polyacrylates and maleic
anhydride-acrylic acid copolymers previously mentioned as builders, as
well as copolymers of maleic anhydride with ethylene, methylvinyl ether or
methacrylic acid, the maleic anhydride constituting at least 20 mole
percent of the copolymer. These materials are normally used at levels of
from 0.5% to 10% by weight, more preferably from 0.75% to 8%, most
preferably from 1% to 6% by weight of the composition.
Preferred optical brighteners are anionic in character, examples of which
are disodium
4,4'-bis-(2-diethanolamino-4-anilino-s-triazin-6-ylamino)stilbene-2:2'disu
lphonate, disodium 4,4'-
bis-(2-morpholino-4-anilino-s-triazin-6-ylamino-stilbene-2:2'-disulphonate
, disodium
4,4'-bis-(2,4-dianilino-s-triazin-6-ylamino)stilbene-2:2'-disulphonate,
monosodium 4',4"-bis-(2,4-dianilino-s-tri-azin-6
ylamino)stilbene-2-sulphonate, disodium
4,4'-bis-(2-anilino-4-(N-methyl-N-2-hydroxyethylamino)-s-triazin-6-ylamino
)stilbene-2,2'-disulphonate, di-sodium 4,4'-bis-(4-phenyl-2,
1,3-triazol-2-yl)-stilbene-2,2'disulphonate, di-so-dium
4,4'bis(2-anilino-4-(1-methyl-2-hydroxyethylamino)-s-triazin-6-
ylami-no)stilbene-2,2'disulphonate, sodium
2(stilbyl-4"-(naphtho-,1',2':4,5)1,2,3 - triazole-2"-sulphonate and
4,4'-bis(2-sulphostyryl)biphenyl.
Other useful polymeric materials are the polyethylene glycols, particularly
those of molecular weight 1000-10000, more particularly 2000 to 8000 and
most preferably about 4000. These are used at levels of from 0.20% to 5%
more preferably from 0.25% to 2.5% by weight. These polymers and the
previously mentioned homo- or co-polymeric polycarboxylate salts are
valuable for improving whiteness maintenance, fabric ash deposition, and
cleaning performance on clay, proteinaceous and oxidizable soils in the
presence of transition metal impurities.
Soil release agents useful in compositions of the present invention are
conventionally copolymers or terpolymers of terephthalic acid with
ethylene glycol and/or propylene glycol units in various arrangements.
Examples of such polymers are disclosed in the commonly assigned U.S. Pat.
Nos. 4,116,885 and 4,711,730 and European Published Patent Application No.
0 272 033. A particular preferred polymer in accordance with EP-A-0 272
033 has the formula
(CH.sub.3 (PEG).sub.43).sub.0.75 (POH).sub.0.25 ›T-PO).sub.2.8
(T-PEG).sub.0.4 !T(PO-H).sub.0.25 ((PEG).sub.43 CH.sub.3).sub.0.75
where PEG is --(OC.sub.2 H.sub.4)O--,PO is (OC.sub.3 H.sub.6 O) and T is
(pcOC.sub.6 H.sub.4 CO).
Also very useful are modified polyesters as random copolymers of dimethyl
terephthalate, dimethyl sulfoisophthalate, ethylene glycol and 1-2 propane
diol, the end groups consisting primarily of sulphobenzoate and
secondarily of mono esters of ethylene glycol and/or propane-diol. The
target is to obtain a polymer capped at both end by sulphobenzoate groups,
"primarily", in the present context most of said copolymers herein will be
end-capped by sulphobenzoate groups. However, some copolymers will be less
than fully capped, and therefore their end groups may consist of monoester
of ethylene glycol and/or propane 1-2 diol, thereof consist "secondarily"
of such species.
The selected polyesters herein contain about 46% by weight of dimethyl
terephthalic acid, about 16% by weight of propane -1.2 diol, about 10% by
weight ethylene glycol about 13% by weight of dimethyl sulfobenzoic acid
and about 15% by weight of sulfoisophthalic acid, and have a molecular
weight of about 3.000. The polyesters and their method of preparation are
described in detail in EPA 311 342.
Fabric softening agents can also be incorporated into laundry detergent
compositions in accordance with the present invention. These agents may be
inorganic or organic in type. Inorganic softening agents are exemplified
by the smectite clays disclosed in GB-A-1 400 898 and in U.S. Pat. No.
5,019,292. Organic fabric softening agents include the water insoluble
tertiary amines as disclosed in GB-A1 514 276 and EP-B0 011 340 and their
combination with mono C12-C14 quaternary ammonium salts are disclosed in
EP-B-0 026 527 and EP-B-0 026 528 and di-long-chain amides as disclosed in
EP-B-0 242 919. Other useful organic ingredients of fabric softening
systems include high molecular weight polyethylene oxide materials as
disclosed in EP-A-0 299 575 and 0 313 146.
Levels of smectite clay are normally in the range from 5% to 15%, more
preferably from 8% to 12% by weight, with the material being added as a
dry mixed component to the remainder of the formulation. Organic fabric
softening agents such as the water-insoluble tertiary amines or dilong
chain amide materials are incorporated at levels of from 0.5% to 5% by
weight, normally from 1% to 3% by weight whilst the high molecular weight
polyethylene oxide materials and the water soluble cationic materials are
added at levels of from 0.1% to 2%, normally from 0.15% to 1.5% by weight.
These materials are normally added to the spray dried portion of the
composition, although in some instances it may be more convenient to add
them as a dry mixed particulate, or spray them as molten liquid on to
other solid components of the composition.
The present invention also relates to a process for inhibiting dye transfer
from one fabric to another of solubilized and suspended dyes encountered
during fabric laundering operations involving colored fabrics.
The detergent compositions according to the present invention may comprise
from 0.001% to 10 %, preferably from 0.01% to 2%, more preferably from
0.05% to 1% by weight of polymeric dye transfer inhibiting agents. Said
polymeric dye transfer inhibiting agents are normally incorporated into
detergent compositions in order to inhibit the transfer of dyes from
colored fabrics onto fabrics washed therewith. These polymers have the
ability to complex or adsorb the fugitive dyes washed out of dyed fabrics
before the dyes have the opportunity to become attached to other articles
in the wash.
Especially suitable polymeric dye transfer inhibiting agents are polyamine
N-oxide polymers, copolymers of N-vinylpyrrolidone and N-vinylimidazole,
polyvinylpyrrolidone polymers, polyvinyloxazolidones and
polyvinylimidazoles or mixtures thereof.
The polyamine N-oxide polymers suitable for use contain units having the
following structure formula:
##STR4##
wherein P is a polymerisable unit, whereto the R--N--O group can be
attached to or wherein the R--N--O group forms part of the polymerisable
unit or a combination of both.
A is NC(O), CO.sub.2, C(O), --O--, --S--, --N--; x is 0 or 1;
R are aliphatic, ethoxylated aliphatics, aromatic, heterocyclic or
alicyclic groups or any combination thereof whereto the nitrogen of the
N--O group can be attached or wherein the nitrogen of the N--O group is
part of these groups.
The N--O group can be represented by the following general structures:
##STR5##
wherein R1, R2, and R3 are aliphatic groups, aromatic, heterocyclic or
alicyclic groups or combinations thereof; x or/and y or/and z is 0 or 1
and wherein the nitrogen of the N--O group can be attached or wherein the
nitrogen of the N--O group forms part of these groups.
The N--O group can be part of the polymerisable unit (P) or can be attached
to the polymeric backbone or a combination of both. Suitable polyamine
N-oxides wherein the N--O group forms pan of the polymerisable unit
comprise polyamine N-oxides wherein R is selected from aliphatic,
aromatic, alicyclic or heterocyclic groups.
One class of said polyamine N-oxides comprises the group of polyamine
N-oxides wherein the nitrogen of the N--O group forms part of the R-group.
Preferred polyamine N-oxides are those wherein R is a heterocyclic group
such as pyrridine, pyrrole, imidazole, pyrrolidine, piperidine, quinoline,
acridine and derivatives thereof.
Another class of said polyamine N-oxides comprises the group of polyamine
N-oxides wherein the nitrogen of the N--O group is attached to the
R-group.
Other suitable polyamine N-oxides are the polyamine oxides whereto the N--O
group is attached to the polymerisable unit.
Preferred class of these polyamine N-oxides are the polyamine N-oxides
having the general formula (I) wherein R is an aromatic, heterocyclic or
alicyclic groups wherein the nitrogen of the N--O functional group is part
of said R group.
Examples of these classes are polyamine oxides wherein R is a heterocyclic
compound such as pyrridine, pyrrole, imidazole and derivatives thereof.
Another preferred class of polyamine N-oxides are the polyamine oxides
having the general formula (I) wherein R are aromatic, heterocyclic or
alicyclic groups wherein the nitrogen of the N--O functional group is
attached to said R groups.
Examples of these classes are polyamine oxides wherein R groups can be
aromatic such as phenyl.
Any polymer backbone can be used as long as the amine oxide polymer formed
is water-soluble and has dye transfer inhibiting properties. Examples of
suitable polymeric backbones are polyvinyls, polyalkylenes, polyesters,
polyethers, polyamide, polyimides, polyacrylates and mixtures thereof.
The amine N-oxide polymers of the present invention typically have a ratio
of amine to the amine N-oxide of 10:1 to 1:1000000. However the amount of
amine oxide groups present in the polyamine oxide polymer can be varied by
appropriate copolymerization or by appropriate degree of N-oxidation.
Preferably, the ratio of amine to amine N-oxide is from 2:3 to 1:1000000.
More preferably from 1:4 to 1:1000000, most preferably from 1:7 to
1:1000000. The polymers of the present invention actually encompass random
or block copolymers where one monomer type is an amine N-oxide and the
other monomer type is either an amine N-oxide or not. The amine oxide unit
of the polyamine N-oxides has a PKa<10, preferably PKa<7, more preferred
PKa<6.
The polyamine oxides can be obtained in almost any degree of
polymerisation. The degree of polymerisation is not critical provided the
material has the desired water-solubility and dye-suspending power.
Typically, the average molecular weight is within the range of 500 to
1000,000; preferably from 1,000 to 50,000, more preferably from 2,000 to
30,000, most preferably from 3,000 to 20,000.
The N-vinylimidazole N-vinylpyrrolidone polymers which may be used in the
present invention have an average molecular weight range from
5,000-1,000,000, preferably from 20,000-200,000.
Highly preferred polymers for use in detergent compositions according to
the present invention comprise a polymer selected from N-vinylimidazole
N-vinylpyrrolidone copolymers wherein said polymer has an average
molecular weight range from 5,000 to 50,000 more preferably from 8,000 to
30,000, most preferably from 10,000 to 20,000.
The average molecular weight range was determined by light scattering as
described in Barth H. G. and Mays J. W. Chemical Analysis Vol 113,"Modern
Methods of Polymer Characterization".
Highly preferred N-vinylimidazole N-vinylpyrrolidone copolymers have an
average molecular weight range from 5,000 to 50,000; more preferably from
8,000 to 30,000; most preferably from 10,000 to 20,000.
The N-vinyllmidazole N-vinylpyrrolidone copolymers characterized by having
said average molecular weight range provide excellent dye transfer
inhibiting properties while not adversely affecting the cleaning
performance of detergent compositions formulated therewith.
The N-vinylimidazole N-vinylpyrrolidone copolymer of the present invention
has a molar ratio of N-vinylimidazole to N-vinylpyrrolidone from 1 to 0.2,
more preferably from 0.8 to 0.3, most preferably from 0.6 to 0.4.
The detergent compositions of the present invention may also utilize
polyvinylpyrrolidone ("PVP") having an average molecular weight of from
about 2,500 to about 400,000, preferably from about 5,000 to about
200,000, more preferably from about 5,000 to about 50,000, and most
preferably from about 5,000 to about 15,000. Suitable
polyvinylpyrrolidones are commercially vailable from ISP Corporation, New
York, N.Y. and Montreal, Canada under the product names PVP K-15
(viscosity molecular weight of 10,000), PVP K-30 (average molecular weight
of 40,000), PVP K-60 (average molecular weight of 160,000), and PVP K-90
(average molecular weight of 360,000). Other suitable
polyvinylpyrrolidones which are commercially available from BASF
Cooperation include Sokalan HP 165 and Sokalan HP 12;
polyvinylpyrrolidones known to persons skilled in the detergent field (see
for example EP-A-262,897 and EP-A-256,696).
The detergent compositions of the present invention may also utilize
polyvinyloxazolidone as a polymeric dye transfer inhibiting agent. Said
polyvinyloxazolidones have an average molecular weight of from about 2,500
to about 400,000, preferably from about 5,000 to about 200,000, more
preferably from about 5,000 to about 50,000, and most preferably from
about 5,000 to about 15,000.
The detergent compositions of the present invention may also utilize
polyvinylimidazole as polymeric dye transfer inhibiting agent. Said
polyvinylimidazoles have an average about 2,500 to about 400,000,
preferably from about 5,000 to about 200,000, more preferably from about
5,000 to about 50,000, and most preferably from about 5,000 to about
15,000.
Method of Washing
The process described herein comprises contacting fabrics with a laundering
solution in the usual manner and exemplified hereunder.
The process of the invention is conveniently carried out in the course of
the cleaning process. The method of cleaning is preferably carried out at
5.degree. C. to 95 .degree. C., especially between 10.degree. C. and
60.degree. C. The pH of the treatment solution is preferably from 7 to 11,
especially from 7.5 to 10.5.
The following examples are meant to exemplify compositions of the present
invention, but are not necessarily meant to limit or otherwise define the
scope of the invention.
In the detergent compositions, the abbreviated component identifications
have the following meanings:
LAS: Sodium linear C.sub.12 alkyl benzene sulphonate
TAS: Sodium tallow alkyl sulphate
XYAS: Sodium C.sub.1X -C.sub.1Y alkyl sulfate
SAS: C.sub.12 -C.sub.14 secondary (2,3) alkyl sulfate in the form of the
sodium salt.
APG: Alkyl polyglycoside surfactant of formula C.sub.12 -(glycosyl).sub.x,
where x is 1.5.
AEC: Alkyl ethoxycarboxylate surfactant of formula C.sub.12 ethoxy (2)
carboxylate.
SS: Secondary soap surfactant of formula 2-butyl octanoic acid
25EY: A C.sub.12 -C.sub.15 predominantly linear primary alcohol condensed
with an average of Y moles of ethylene oxide
45EY: A C.sub.14 -C.sub.15 predominantly linear primary alcohol condensed
with an average of Y moles of ethylene oxide
XYEZS: C.sub.1X -C.sub.1Y sodium alkyl sulfate condensed with an average of
Z moles of ethylene oxide per mole
Nonionic: C.sub.13 -C.sub.15 mixed ethoxylated/propoxylated fatty alcohol
with an average degree of ethoxylation of 3.8 and an average degree of
propoxylation of 4.5 sold under the tradename Plurafax LF404 by BASF Gmbh
CFAA: C.sub.12 -C.sub.14 alkyl N-methyl glucamide
TFAA: C.sub.16 -C.sub.18 alkyl N-methyl glucamide.
Silicate: Amorphous Sodium Silicate (SiO.sub.2 :Na.sub.2 O ratio=2.0)
NaSKS-6: Crystalline layered silicate of formula .delta.-Na.sub.2 Si.sub.2
O.sub.5
Cabonate: Anhydrous sodium carbonate
Phosphate: Sodium tripolyphosphate
MA/AA: Copolymer of 1:4 maleic/acrylic acid, average molecular weight about
80,000
Polyacrylate: Polyacrylate homopolymer with an average molecular weight of
8,000 sold under the tradename PA30 by BASF GmbH
Zeolite A: Hydrated Sodium Aluminosilicate of formula Na.sub.12 (AlO.sub.2
SiO.sub.2).sub.12.27H.sub.2 O having a primary particle size in the range
from 1 to 10 micrometers
Citrate: Tri-sodium citrate dihydrate
Citric: Citric Acid
Perborate: Anhydrous sodium perborate monohydrate bleach, empirical formula
NaBO.sub.2.H.sub.2 O.sub.2
PB4: Anhydrous sodium perborate tetrahydrate
Percarbonate: Anhydrous sodium percarbonate bleach of empirical formula
2Na.sub.2 CO.sub.3.3H.sub.2 O.sub.2
TAED: Tetraacetyl ethylene diamine
Paraffin: Paraffin oil sold under the tradename Winog 70 by Wintershall.
Xylanase: Xylanolytic enzyme sold under the tradenames Pulpzyme HB or SP431
by Novo Nordisk A/S or Lyxasan (Gist-Brocades) or Optipulp or Xylanase
(Solvay).
Protease: Proteolytic enzyme sold under the tradename Savinase by Novo
Nordisk A/S. Protease D: Proteolytic enzyme which is a Bacillus lentus
subtilisin variant N76D/S103 A/V1041, according to the numbering of
Bacillus amyloliquefaciens subtilisin.
Amylase: Amylolytic enzyme sold under the tradename Termamyl by Novo
Nordisk A/S
Lipase: Lipolytic enzyme sold under the tradename Lipolase by Novo Nordisk
A/S
D96Lipase: Variant of the native lipase derived from Humicola lanuginosa
Peroxidase: Peroxidase enzyme
Cellulase: Cellulosic enzyme sold under the tradename Carezyme or Celluzyme
by Novo Nordisk A/S.
CMC: Sodium carboxymethyl cellulose
HEDP: 1,1-hydroxyethane diphosphonic acid
DETPMP: Diethylene triamine penta (methylene phosphonic acid), marketed by
Monsanto under the Trade name Dequest 2060
PVP: Polyvinyl pyrrolidone polymer
EDDS: Ethylenediamine -N, N'- disuccinic acid, ›S,S! isomer in the form of
the sodium salt.
Suds Suppressor: 25% paraffin wax Mpt 50.degree. C., 17% hydrophobic
silica, 58% paraffin oil.
Granular Suds Suppressor: 12% Silicone/silica, 18% stearyl alcohol,70%
starch in granular form
SCS: Sodium cumene sulphonate
Sulphate: Anhydrous sodium sulphate.
HMWPEO: High molecular weight polyethylene oxide
PGMS: Polyglycerol monostearate having a tradename of Radiasuff248
TAE 25: Tallow alcohol ethoxylate (25)
In the following examples all levels of enzyme quoted are expressed as %
active enzyme by weight of the composition:
EXAMPLE 1
A compact granular fabric cleaning composition in accord with the invention
is prepared as follows:
______________________________________
45AS 9.0
25E3S 2.3
25E5 4.4
TFAA 1.9
Zeolite A 14.1
NaSKS-6 11.9
Citric acid 3.2
Carbonate 7.1
MA/AA 4.5
CMC 0.4
Poly(4-vinylpyridine)-N-oxide/
0.027
copolymer of vinylimidazole and vinylpyrrolidone
D96L Lipase To provide 5000
LU/L wash
Protease 0.03
Cellulase 0.0006
Amylase 0.006
TAED 4.9
Percarbonate 22.3
Granular suds suppressor
3.6
water/minors Up to 100%
______________________________________
Use of this laundry detergent composition to wash fabrics identified by
consumers as having dingy soil buildup results in improved dingy clean-up
of these fabrics versus the dingy clean-up achieved using this composition
comprising only D96L Lipase or Protease.
EXAMPLE 2
A granular fabric cleaning composition in accord with the invention is
prepared as follows:
______________________________________
LAS 10.3
45AS 6.6
25AE3S 1.8
Zeolite A 26.3
Carbonate 26.3
PEG 1.7
Polyacrylate 3.2
Na2SO4 10.3
23E6.5 0.5
D96L Lipase To provide 300 LU/L wash
Protease D To provide 0.1 mg active protease/L wash
Water and minors
up to 100%
______________________________________
Use of this laundry detergent composition to wash fabrics identified by
consumers as having dingy soil buildup results in improved dingy clean-up
of these fabrics versus the dingy clean-up achieved using this composition
comprising only D96L Lipase or Protease D.
Similar results can be observed substituting into this formula Lipase for
the D96L Lipolase, or by using both Lipase and D96L Lipase; and by
substituting Protease, Maxacal.RTM., Protease A, Protease B, or Protease
C, or mixtures thereof with Protease D.
EXAMPLE 3
Granular fabric cleaning compositions in accord with the invention are
prepared as follows:
______________________________________
I II III IV
______________________________________
LAS 22.0 22.0 22.0 22.0
Phosphate 23.0 23.0 23.0 23.0
Carbonate 23.0 23.0 23.0 23.0
Silicate 14.0 14.0 14.0 14.0
Zeolite A 8.2 8.2 8.2 8.2
DETPMP 0.4 0.4 0.4 0.4
Sodium Sulfate
5.5 5.5 5.5 5.5
Protease 0.01 -- 0.01 0.005
Protease D
-- 0.02 0.01 --
Xylanase 0.04 -- -- --
D96L Lipase
0.005 -- 0.002 0.005
Lipase -- 0.005 -- --
Cellulase 0.001 -- -- 0.001
Amylase 0.01 -- 0.01 --
Pectinase 0.02 -- -- --
Water/minors
Up to 100%
______________________________________
EXAMPLE 4
Granular fabric cleaning compositions in accord with the invention are
prepared as follows:
______________________________________
I II III IV
______________________________________
LAS 12.0 12.0 12.0 12.0
Zeolite A 26.0 26.0 26.0 26.0
SS 4.0 4.0 4.0 4.0
SAS 5.0 5.0 5.0 5.0
Citrate 5.0 5.0 5.0 5.0
Sodium Sulfate
17.0 17.0 17.0 28.0
Perborate 16.0 16.0 16.0 --
TAED 5.0 5.0 5.0 --
Xylanase 0.20 -- -- --
Protease 0.06 -- 0.02 0.08
Protease D
-- 0.03 0.01 --
D96L Lipase
0.005 0.0003 0.01 0.005
Cellulase 0.001 -- -- 0.001
Amylase 0.01 -- 0.01 --
Pectinase 0.02 -- -- --
Water/minors
Up to 100%
______________________________________
EXAMPLE 5
Granular fabric cleaning compositions in accord with the invention which
are especially useful in the laundering of coloured fabrics are prepared
as follows:
______________________________________
LAS 11.4 10.7 --
TAS 1.8 2.4 --
TFAA -- -- 4.0
45AS 3.0 3.1 10.0
45E7 4.0 4.0 --
25E3S -- -- 3.0
68E11 1.8 1.8 --
25E5 -- -- 8.0
Citrate 14.0 15.0 7.0
Carbonate -- -- 10
Citric acid 3.0 2.5 3.0
Zeolite A 32.5 32.1 25.0
Na-SKS-6 -- -- 9.0
MA/AA 5.0 5.0 5.0
DETPMP 1.0 0.2 0.8
Xylase 0.01 -- --
Protease 0.02 -- 0.01
Protease D -- 0.02 --
D96L Lipase 0.0005 0.01 0.005
Amylase 0.03 0.03 0.005
Pectinase 0.01 -- --
Cellulase 0.005 -- 0.001
Silicate 2.0 2.5 --
Sulphate 3.5 5.2 3.0
PVP 0.3 0.5 --
Poly(4-vinylpyridine)-N-oxide/
-- -- 0.2
copolymer of vinyl-imidazole
and vinyl-pyrrolidone
Perborate 0.5 1.0 --
Peroxidase 0.01 0.01 --
Phenol sulfonate
0.1 0.2 --
Water/Minors Up to 100%
______________________________________
EXAMPLE 6
Granular fabric cleaning compositions in accord with the invention are
prepared as follows:
______________________________________
LAS 6.5 8.0
Sulfate 15.0 18.0
Zeolite A 26.0 22.0
Sodium nitrilotriacetate
5.0 5.0
PVP 0.5 0.7
TAED 3.0 3.0
Boric acid 4.0 --
Perborate 0.5 1.0
Phenol sulphonate 0.1 --
Protease D 0.06 0.02
Xylanase 0.01 --
Silicate 5.0 5.0
Carbonate 15.0 15.0
Peroxidase 0.1 --
D96L Lipase 0.001 0.0005
Amylase 0.01 0.01
Pectinase 0.02 --
Cellulase 0.005 0.002
Water/minors Up to 100%
______________________________________
EXAMPLE 7
A granular fabric cleaning compositions in accord with the invention which
provide "softening through the wash" capability are prepared as follows:
______________________________________
45AS -- 10.0
LAS 7.6 --
68AS 1.3 --
45E7 4.0 --
25E3 -- 5.0
Coco-alkyl-dimethyl hydroxy-
1.4 1.0
ethyl ammonium chloride
Citrate 5.0 3.0
Na-SKS-6 -- 11.0
Zeolite A 15.0 15.0
MA/AA 4.0 4.0
DETPMP 0.4 0.4
Perborate 15.0 --
Percarbonate -- 15.0
TAED 5.0 5.0
Smectite clay 10.0 10.0
HMWPEO -- 0.1
Protease 0.02 0.01
D96L Lipase 0.002 0.0003
Amylase 0.03 0.005
Xylanase 0.03 --
Cellulase 0.02 0.001
Pectinase 0.01 --
Silicate 3.0 5.0
Carbonate 10.0 10.0
Granular suds suppressor
1.0 4.0
CMC 0.2 0.1
Water/minors Up to 100%
______________________________________
EXAMPLE 8
Heavy duty liquid fabric cleaning compositions suitable for use in the
pretreatment of stained fabrics, and for use in a machine laundering
method, in accord with the invention are prepared as follows:
______________________________________
I II III IV V
______________________________________
24AS 20.0 20.0 20.0 20.0 20.0
SS 5.0 5.0 5.0 5.0 5.0
Citrate 1.0 1.0 1.0 1.0 1.0
12E.sub.3 13.0 13.0 13.0 13.0 13.0
Monethanolamine
2.5 2.5 2.5 2.5 2.5
Xylanase 0.02 -- -- -- --
Protease 0.005 0.03 0.02 0.04 0.01
D96L Lipase
0.002 0.01 0.0005 0.001 0.004
Amylase 0.005 0.005 -- -- 0.004
Cellulase 0.04 -- 0.01 -- --
Pectinase 0.02 0.02 -- -- --
Water/propylene glycol/ethanol (100:1:1)
______________________________________
EXAMPLE 9
Heavy duty liquid fabric cleaning compositions in accord with the invention
are prepared as follows:
______________________________________
I II III IV
______________________________________
LAS acid form -- -- 25.0 --
C.sub.12-14 alkenyl succinic acid
3.0 8.0 10.0 --
Citric acid 10.0 15.0 2.0 2.0
25AS acid form
8.0 8.0 -- 15.0
25AE2S acid form
-- 3.0 -- 4.0
25AE7 -- 8.0 -- 6.0
25AE3 8.0 -- -- --
CFAA -- -- -- 6.0
DETPMP 0.2 -- 1.0 1.0
Fatty acid -- -- -- 10.0
Oleic acid 1.8 -- 1.0 --
Ethanol 4.0 4.0 6.0 2.0
Propanediol 2.0 2.0 6.0 10.0
Xylanase 0.05 -- -- --
Protease D 0.02 0.02 0.02 0.01
Amylase 0.005 0.01 0.005 0.01
D96L Lipase 0.005 0.02 0.005 0.01
Cellulase 0.005 -- -- --
Pectinase 0.02 -- -- --
Coco-alkyl dimethyl
-- -- 3.0 --
hydroxy ethyl
ammonium chloride
Smectite clay -- -- 5.0 --
PVP 1.0 2.0 -- --
Perborate -- 1.0 -- --
Phenol sulphonate
-- 0.2 -- --
Peroxidase -- 0.01 -- --
NaOH Up to pH 7.5
Waters/minors Up to 100%
______________________________________
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